CN102762629B - Thermosetting epoxy resin composition - Google Patents
Thermosetting epoxy resin composition Download PDFInfo
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- CN102762629B CN102762629B CN201180007646.7A CN201180007646A CN102762629B CN 102762629 B CN102762629 B CN 102762629B CN 201180007646 A CN201180007646 A CN 201180007646A CN 102762629 B CN102762629 B CN 102762629B
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- epoxy resin
- represented
- sulfonium salt
- salt compound
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 64
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 229920001187 thermosetting polymer Polymers 0.000 title abstract 3
- -1 sulfonium salt compound Chemical class 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 150000001875 compounds Chemical group 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 abstract 2
- 230000009477 glass transition Effects 0.000 abstract 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 abstract 1
- 230000007704 transition Effects 0.000 description 25
- 238000001879 gelation Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 3
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- FYSNRPHRLRVCSW-UHFFFAOYSA-N dodecasodium;tetraborate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] FYSNRPHRLRVCSW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XVYGMGNVWKBMCH-NLGIKVKISA-N BC(C)(C)[C@H](C[C@@H](C)F)/C=C(\C(C)=C)/F Chemical compound BC(C)(C)[C@H](C[C@@H](C)F)/C=C(\C(C)=C)/F XVYGMGNVWKBMCH-NLGIKVKISA-N 0.000 description 1
- DJRGUQNUDGFOFG-UHFFFAOYSA-N CCC(C)(S(C)C(C)C1=CC=[I]C=C1C)[IH]C=CC(C)O Chemical compound CCC(C)(S(C)C(C)C1=CC=[I]C=C1C)[IH]C=CC(C)O DJRGUQNUDGFOFG-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- FWQHRZXEQNUCSY-UHFFFAOYSA-N tert-butyl N-[2-(ethoxycarbonylamino)-5-[(4-fluorophenyl)methyl-prop-2-ynylamino]phenyl]carbamate Chemical compound CCOC(=O)NC1=C(C=C(C=C1)N(CC#C)CC2=CC=C(C=C2)F)NC(=O)OC(C)(C)C FWQHRZXEQNUCSY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
Disclosed is a thermosetting epoxy resin composition having a high glass transition temperature while maintaining superior curing properties. Specifically disclosed is a thermosetting epoxy resin composition containing an epoxy resin (A) and a sulfonium salt compound (B) represented by formulas (I) and (II) as a curing agent. In formulas (I) and (II), R1 and R3 are the same or different and are one selected from a group formed from groups represented by formula (1), groups represented by formula (2), and groups represented by formula (3); R2 and R4 are the same or different, and are hydrogen atoms or alkyl groups; and X is a compound represented by formula (4). In formulas (1), (2), and (3), R5 is the same or different and is an optionally substituted aromatic hydrocarbon group or aliphatic hydrocarbon group, or a group in which an optionally substituted aromatic hydrocarbon group or aliphatic hydrocarbon group is bonded with a carboxyl group or sulfonyl group.
Description
Technical field
The present invention relates to heat-curable epoxy resin composition.
Background technology
As the solidifying agent of epoxy resin, disclose the sulfonium salt compound (for example,, with reference to patent documentation 1) with naphthyl or benzyl.
The composition epoxy resin that utilization has the sulfonium salt compound of naphthyl has good solidified nature.
Utilization has the composition epoxy resin of the sulfonium salt compound of benzyl to be compared with the composition that utilization has the sulfonium salt compound of naphthyl, although excellent in stability, solidified nature is poor.
Above two kinds of solidifying agent are suitably separately used according to the purposes of composition epoxy resin etc.
Patent documentation 1: JP 2008-308596 communique
Summary of the invention
But, use the situation of two kinds of compounds to compare with situation about using separately respectively simultaneously, there is the tendency that effect that each compound plays on the contrary can be impaired.
The object of the present invention is to provide a kind of high heat-curable epoxy resin composition of second-order transition temperature of cured article when maintaining good solidified nature.
In order to solve the described problem inventor, carried out conscientious research, found that, second-order transition temperature when utilization has the composition epoxy resin hot setting of sulfonium salt compound of naphthyl is low, in addition, utilizing the composition epoxy resin of the sulfonium salt compound with benzyl is that the second-order transition temperature of cured article is high.And, the inventor further conscientiously finds after research, while using the sulfonium salt compound being represented by following formula (I) and the sulfonium salt compound being represented by following formula (II) as solidifying agent simultaneously, obtaining unexpectedly solidified nature does not have the high composition epoxy resin of second-order transition temperature of impaired and cured article, has completed thus the present invention.
[changing 1]
[changing 2]
[in formula (I) and formula (II), R
1and R
3identical or not identical, be select from the group that hydroxyl, the base being represented by following formula (1), the base being represented by following formula (2) and the base that represented by following formula (3) form a kind of, R
2and R
4identical or not identical, be hydrogen atom or alkyl, X is the compound being represented by following formula (4).]
[changing 3]
R
5O- (1)
[changing 4]
[changing 5]
[in formula (1), (2) and (3), R
5for identical or not identical, be can there is substituent aromatic hydrocarbyl or aliphatic alkyl or can there is substituent aromatic hydrocarbyl or base that aliphatic alkyl and carboxyl or alkylsulfonyl are combined into.]
[changing 6]
That is, the invention provides a kind of heat-curable epoxy resin composition of the sulfonium salt compound (B) that comprises epoxy resin (A) and represented by formula (I) and formula (II) respectively.
Second-order transition temperature while solidifying when heat-curable epoxy resin composition of the present invention maintains good solidified nature is high.
Accompanying drawing explanation
Fig. 1 is for representing gelation time at 150 ℃ in each composition epoxy resin of embodiments of the invention and comparative example and the graphic representation of the relation between second-order transition temperature.
Embodiment
Below, describe heat-curable epoxy resin composition of the present invention in detail.
Heat-curable epoxy resin composition of the present invention comprises epoxy resin A and as the sulfonium salt compound B of solidifying agent.
Epoxy resin so long as have two above epoxy group(ing) and be just not particularly limited, can be used existing known epoxy resin.Particularly, can enumerate as bisphenol A type epoxy resin, dicyclopentadiene-type epoxy resin, diaminodiphenyl-methane type epoxy resin, amino-benzene phenol-type epoxy resin, naphthalene type epoxy resin, phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, A Hydrogenated Bisphenol A type epoxy resin, alicyclic epoxy resin.
In addition, in order to give pliability to epoxy resin, can add propylene oxide compound or vinyl ether compound to epoxy resin.
Epoxy resin can be respectively separately with or two or more combinations are used.
As solidifying agent, use two kinds of sulfonium salt compounds that represented by formula (I) and formula (II) respectively.In formula (I) and formula (II), R
1, R
3identical or not identical, be select in base, the base of formula (2) expression and the group of the base formation that formula (3) represents from representing in hydroxyl, formula (1) a kind of.
R
1, R
3configuration can be to sulfonium cation, be respectively any one in ortho position, a position, contraposition, but second-order transition temperature good from the viewpoint of solidified nature, cured article to be high, for sulfonium cation, is preferably contraposition.
In formula (1), (2) and (3), R
5identical or not identical, be can there is substituent aromatic hydrocarbyl or aliphatic alkyl or can there is substituent aromatic hydrocarbyl or base that aliphatic alkyl and carboxyl or alkylsulfonyl are combined into.As aromatic hydrocarbyl, can enumerate as aryl, aralkyl etc.As aryl, the quantity that can enumerate carbon is 6～14, preferably 6～10 aryl.For example, phenyl, naphthyl, xenyl, anthryl, phenanthryl etc.As aralkyl, the quantity that can enumerate carbon is 7～13, preferably 7～11 aralkyl.For example, can enumerate benzyl, styroyl etc.As thering is substituent aromatic hydrocarbyl, on this aromatic hydrocarbyl, during in conjunction with carboxyl or alkylsulfonyl, can enumerate as tolyl, xylyl, hydroxyphenyl.What in tolyl, preferably utilize is p-tolyl.
As aliphatic alkyl, can enumerate saturated or undersaturated alkyl.The quantity that can enumerate carbon as saturated hydrocarbyl is 1～18, preferably 1～6 alkyl.For example, the straight chain of methyl, ethyl, n-propyl group, sec.-propyl, n-butyl, isobutyl-, sec-butyl, t-butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl etc. or the alkyl of difference shape, and the cycloalkyl such as cyclopropyl, cyclobutyl, cyclohexyl, suberyl, ring octyl group.
As unsaturated alkyl, the quantity that can enumerate carbon is 2～18, and the quantity of preferably 2～6 univalent unsaturated hydrocarbon radical, and carbon is 2～18, preferably 2～6 divalence unsaturated alkyl.As univalent unsaturated hydrocarbon radical, can enumerate as the thiazolinyl of the straight chains such as vinyl, 1-propenyl, allyl group, pseudoallyl, 1-butylene base, crotyl, pentenyl, hexenyl and difference shape, and the cycloalkenyl group such as cyclopentenyl, cyclohexenyl.As divalence unsaturated alkyl, can enumerate as alkylene groups such as vinylene etc.
When carboxyl or alkylsulfonyl are combined with aromatic hydrocarbyl or aliphatic alkyl, in formula (1), be combined with Sauerstoffatom, in formula (2), be combined with carbon atom, in formula (3), be combined with nitrogen-atoms.Carboxyl is combined with aromatic hydrocarbyl or aliphatic alkyl by its carbon atom.
In formula (1), as R
5can enumerate as methyl, methoxyl group, phenyl, phenoxy group, wherein, what preferably use is methyl.In formula (2), as R
5, can enumerate as methyl, methoxyl group, phenoxy group, benzyl, phenyl, wherein, what preferably use is methoxyl group.In formula (3), as R
5can enumerate as methyl, methoxyl group, phenyl, phenoxy group, phenylene, tosyl group, what in tosyl group, preferably use is p-tosyl group.
In formula (I) and formula (II), R
2and R
4for identical or not identical, be hydrogen atom or alkyl.As alkyl, what preferably enumerate is that carbonatoms is 1～6 alkyl.For example, can enumerate methyl, ethyl, n-propyl group, sec.-propyl etc.As R
2and R
4, particularly preferably be hydrogen atom or methyl.
The sulfonium salt compound being represented by formula (I) and formula (II) can with separately with or two or more combination use.
As the sulfonium salt compound being represented by formula (I), can enumerate the compound as represented by following formula (Ia) and formula (Ib).
[changing 7]
[changing 8]
As the sulfonium salt compound being represented by formula (II), can enumerate the compound as represented by following formula (IIa).
[changing 9]
The compound being represented by formula (I) and formula (II), is not particularly limited about its manufacture.For example, can obtain by the method for existing known (for example,, about the compound of formula (I), with reference to the reference example 1 of JP 2008-308596 communique, about the compound of formula (II), with reference to the reference example 3 with communique).In addition, the compound that part is represented by formula (I) and formula (II) is to obtain by commercially available product.
Second-order transition temperature better from the viewpoint of solidified nature, cured article is higher, the sulfonium salt compound being represented by formula (I) is with respect to the ratio of mixture of the sulfonium salt compound being represented by formula (II), with weight ratio, represent, the preferably value in 0.1～10 scope, the more preferably value in 0.2～5 scope.In addition, extra high from the viewpoint of the second-order transition temperature of cured article, this ratio of mixture represents with weight ratio, preferably the value in 0.1～1 scope.
The combined amount of solidifying agent is that second-order transition temperature better from the viewpoint of solidified nature, cured article is higher, and with respect to epoxy resin 100 weight parts, preferably full sulfonium salt compound is 0.1～10 weight part, more preferably 0.5～5 weight part.
Composition epoxy resin of the present invention, on the basis that comprises epoxy resin, solidifying agent, can also comprise the curing catalysts such as Lewis acid in the scope of not damaging invention effect.
In addition, composition epoxy resin of the present invention, except each above-mentioned composition, can also comprise additive as required.As additive, can enumerate as weighting agent (weighting material), silane coupling agent, reactive thinner, softening agent, thixotropy imparting agent, pigment, dyestuff, protective agent, oxidation inhibitor, antistatic agent, fire retardant, tackifier, dispersion agent, solvent etc.As weighting agent, can enumerate silicon-dioxide, mica etc.
Composition of the present invention is not particularly limited about its manufacture.For example, above-mentioned epoxy resin, solidifying agent and the curing catalyst adding as required,, each composition of additive is mixing and disperse equably fully by utilizing the whipping apptss such as mixed milling machine to carry out under decompression or nitrogen atmosphere gas condition, can be accessed to a liquid type epoxy composition thus.
In addition, composition of the present invention can be manufactured as the binary liquid shape composition of the second liquid (solidifying agent) that for example has the first liquid (host) that comprises epoxy resin and comprise the sulfonium salt compound being represented by formula (I) and formula (II).Additive can be added on the first liquid and/or the second liquid.The first liquid and the second liquid can be respectively under decompression or nitrogen atmosphere gas condition by utilize the whipping apptss such as mixed milling machine carry out fully mixing and equably dispersion manufacture.
Composition of the present invention for example can be used as, medical, packaging for, electric use for, civil construction for, coating for binding agent, transfer roller, fiber and uses with composition with, motion and leisure.Particularly, from the viewpoint of accessing, have the good and productivity of solidified nature and improve and the good high-quality product of physical properties, composition of the present invention is preferably used by binding agent purposes as electronic material.Wherein, more preferably, as the composition of ACF (anisotropic conductive film), use.
Adherend that can be applicable as composition of the present invention, can enumerate as metal, glass, plastics, mortar, concrete, rubber, timber, skin, cloth, paper etc.
The method that composition of the present invention is given to adherend is not particularly limited, and for example, can enumerate existing known method.
Temperature while solidifying composition of the present invention, second-order transition temperature better from the viewpoint of solidified nature, cured article is higher, when using as epoxy resin the bisphenol A type epoxy resin EP4100E being manufactured by ADEKA company, preferably 100～250 ℃, more preferably 120～200 ℃.
In the present invention, solidified nature is evaluated with the gelation time (gelation time) of composition epoxy resin, particularly, and by measuring by the method for peace described later field formula gelation time tester.The gelation time of composition of the present invention for example, while using the bisphenol A type epoxy resin EP4100E of ADEKA company manufacture as epoxy resin, is in 40 seconds, preferably in 30 seconds at 150 ℃.
In addition, in the present invention, second-order transition temperature is particularly equally evaluated by measuring the storage modulus of cured article as described later.The second-order transition temperature of the cured article that curing composition of the present invention obtains, for example, while using the bisphenol A type epoxy resin EP4100E of ADEKA company manufacture as epoxy resin, more than 100 ℃, preferably more than 120 ℃.
Embodiment
Below, with reference to embodiment, illustrate the present invention.
(manufacture of composition epoxy resin)
As embodiment 1～11, comparative example 1～10, each composition shown in following table 1～4 is mixed according to the ratio of mixture shown in table respectively, manufacture thus composition epoxy resin.The numerical value of each composition in table is used in % by weight shared in composition epoxy resin represents except the combined amount of weighting agent, and remaining numerical value represents with weight part.In addition, the amount of solidifying agent is to using the equivalents of its active hydrogen to go out as benchmark.
[table 1]
[table 2]
[table 3]
[table 4]
The details of each composition shown in table 1～4 is as follows.
Epoxy resin: bisphenol A type epoxy resin, epoxy equivalent (weight) 188g/mol (trade(brand)name EP4100E, ADEKA company manufactures)
Solidifying agent (1): the sulfonium salt compound being represented by formula (Ia)
Solidifying agent (2): the sulfonium salt compound being represented by formula (IIa)
Solidifying agent (3): the sulfonium salt compound being represented by formula (Ib)
Solidifying agent (4): the sulfonium salt compound being represented by following formula (manufacture of trade(brand)name SI80L ，San Xin chemical industrial company)
[changing 10]
Solidifying agent (5): the sulfonium salt compound being represented by following formula (manufacture of trade(brand)name SI100L ，San Xin chemical industrial company)
[changing 11]
Silane coupling agent (trade(brand)name KBM403, chemical industrial company of SHIN-ETSU HANTOTAI manufactures)
Weighting agent: spherical silicon dioxide (trade(brand)name SE5050, Admatechs company manufactures)
In addition, about solidifying agent 1, by making 1-(chloromethyl) naphthalene 10g and 4-methylthiophenol 7.9g react under room temperature condition and obtain muriate intermediate in 24 hours, and further intermediate 10g and four (pentafluorophenyl group) Sodium Tetraborate salt brine solution (solids content 10%) 220.16g is obtained by mixing to solidifying agent 1 in methyl alcohol.
About solidifying agent 2, by making benzyl chloride compound 10g and 4-methylthiophenol 11.07g react under room temperature condition and obtain muriate intermediate in 24 hours, and further intermediate 10g and four (pentafluorophenyl group) Sodium Tetraborate salt brine solution (solids content 10%) 263g is obtained by mixing to solidifying agent 2 in methyl alcohol.
Solidifying agent 3 is within 5 hours, to obtain by the solidifying agent 1 of 10g and isocyanic acid p-tolylsulfonyl 2.05g are reacted at ambient temperature.
(evaluation)
For resulting composition epoxy resin, by following method, measure gelation time and storage modulus respectively, thereby evaluated solidified nature and second-order transition temperature.The results are shown in table 1～4 and Fig. 1.Fig. 1 is for representing the scatter diagram of the relation between the gelation time at second-order transition temperature in each composition of embodiment 1～11 and comparative example 1～10 and 150 ℃.The longitudinal axis represents second-order transition temperature, and the value representation second-order transition temperature of top is higher.Transverse axis represents the gelation time at 150 ℃, and the value representation gelation time on the right is shorter, solidified nature is better.
(1) gelation time
To each composition obtaining as described above, utilize peace field formula gelation time tester (Co., Ltd.'s peace field essence mechanism is made manufacturing, No.153 gelation time tester), at 150 ℃, measure gelation time.Peace field formula gelation time tester is, in thermostatic oil bath, at the test tube of putting into sample, makes rotor, when gelation is carried out and while being endowed the moment of torsion of regulation, by magnetic coupling rotor, stops the rotation and device that timer stops.
(2) storage modulus
Each composition obtaining is as described above solidified 1 hour respectively in 150 ℃ of baking ovens.For each cured article, carry out dynamic viscoelastic measurement (Dynamic Mechanical Analysis), that is,, under the condition of 5 ℃/min of deformation rates 0.01%, frequency 10Hz, heat-up rate, from the temperature province of room temperature to 200 ℃, force to uphold vibration and measure storage modulus G '.
From the result shown in table 1 ~ 4, as solidifying agent, composition epoxy resin (the comparative example 1 that comprises the sulfonium salt compound being represented by formula I and do not comprise the sulfonium salt compound being represented by formula II, 3) although gelation time be 40 seconds with interior and solidified nature is good, the second-order transition temperature of cured article does not reach 100 ℃.
In addition, as solidifying agent, comprise by the sulfonium salt compound of formula II and the composition epoxy resin (comparative example 2) that do not comprise the sulfonium salt compound being represented by formula I although second-order transition temperature reaches more than 100 ℃, gelation time surpasses 40 seconds and solidified nature is poor.
In addition, as solidifying agent, composition epoxy resin (comparative example 6 ~ 9) gelation time that comprises other sulfonium salt compound beyond the sulfonium salt compound being represented by formula I and the sulfonium salt compound being represented by formula II surpasses 40 seconds and solidified nature is poor, and wherein the second-order transition temperature of the cured article of comparative example 6,7 does not also reach 100 ℃.
Particularly, as can be seen from Figure 1, the composition of comparative example 6,7 as solidifying agent with whether to comprise the sulfonium salt compound being represented by formula I irrelevant, it is poor on the contrary that the situation of the sulfonium salt compound being represented by formula I with independent use (comparative example 1,3) is compared solidified nature, and the second-order transition temperature of cured article also declines.In addition, the composition of comparative example 8,9 as solidifying agent with whether to comprise the sulfonium salt compound being represented by formula II irrelevant, it is low on the contrary that the situation of the sulfonium salt compound being represented by formula II with independent use (comparative example 2) is compared second-order transition temperature, and solidified nature is variation also.
As solidifying agent, do not comprise the epoxy resin (comparative example 4,5,10) of the sulfonium salt compound being represented by formula I and any formula of formula II, gelation time surpasses 40 seconds and solidified nature is poor, and the second-order transition temperature of cured article does not reach 100 ℃.
Compare with these, as solidifying agent, comprise the composition epoxy resin (embodiment 1 ~ 11) of the sulfonium salt compound being represented by formula I and formula II simultaneously, gelation time is that 40 seconds are following and solidified nature is very good, and the second-order transition temperature of cured article is over 100 ℃.That is, confirmed the following fact: as solidifying agent, by formula I and formula II two sides' sulfonium salt compound is used as solidifying agent, also high composition of the second-order transition temperature of cured article in the time of the solidified nature that obtains unexpectedly remaining good.
Claims (3)
1. a heat-curable epoxy resin composition, is characterized in that, the sulfonium salt compound (B) that comprises epoxy resin (A) and represented by following formula (I) and formula (II) respectively as solidifying agent,
[changing 1]
[changing 2]
In formula (I) and formula (II), R
1and R
3identical or not identical, be select from the group that hydroxyl, the base being represented by following formula (1), the base being represented by following formula (2) and the base that represented by following formula (3) form a kind of, R
2and R
4identical or not identical, be hydrogen atom or alkyl, X is the compound being represented by following formula (4),
[changing 3]
R
5O-(1)
[changing 4]
[changing 5]
In formula (1), (2) and (3), R
5for identical or not identical, be can there is substituent aromatic hydrocarbyl or aliphatic alkyl or can there is substituent aromatic hydrocarbyl or base that aliphatic alkyl and carboxyl or alkylsulfonyl are combined into.
[changing 6]
2. heat-curable epoxy resin composition according to claim 1, it is characterized in that, described epoxy resin (A) with respect to 100 weight parts, described sulfonium salt compound (B) mixes with total amount 0.1～10 weight part, and the sulfonium salt compound being represented by described formula (I) is expressed as 0.1～10 with respect to the ratio of mixture of the sulfonium salt compound being represented by described formula (II) with weight ratio.
3. heat-curable epoxy resin composition according to claim 2, is characterized in that, the sulfonium salt compound being represented by described formula (I) is expressed as 0.1～1 with respect to the ratio of mixture of the sulfonium salt compound being represented by described formula (II) with weight ratio.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-106658 | 2010-05-06 | ||
| JP2010106658 | 2010-05-06 | ||
| JP2010-218445 | 2010-09-29 | ||
| JP2010218445A JP4784698B1 (en) | 2010-05-06 | 2010-09-29 | Thermosetting epoxy resin composition |
| PCT/JP2011/002533 WO2011138868A1 (en) | 2010-05-06 | 2011-05-02 | Thermosetting epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102762629A CN102762629A (en) | 2012-10-31 |
| CN102762629B true CN102762629B (en) | 2014-02-26 |
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| CN201180007646.7A Expired - Fee Related CN102762629B (en) | 2010-05-06 | 2011-05-02 | Thermosetting epoxy resin composition |
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|---|---|
| JP (1) | JP4784698B1 (en) |
| KR (1) | KR101192672B1 (en) |
| CN (1) | CN102762629B (en) |
| WO (1) | WO2011138868A1 (en) |
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| KR101355855B1 (en) | 2011-12-19 | 2014-01-29 | 제일모직주식회사 | Anisotropic conductive film |
| KR101702704B1 (en) | 2013-07-23 | 2017-02-03 | 제일모직주식회사 | Compound comprising phosphonium ion, epoxy resin composition comprising the same and apparatus prepared from using the same |
| WO2015012467A1 (en) * | 2013-07-23 | 2015-01-29 | 제일모직 주식회사 | Compound containing phosphonium ion, epoxy resin composition containing same, and device manufactured by using same |
| KR101969272B1 (en) | 2013-09-25 | 2019-04-15 | 아사히 가세이 이-매터리얼즈 가부시키가이샤 | Onium salt, and composition containing same |
| JPWO2019198378A1 (en) * | 2018-04-13 | 2021-02-12 | 株式会社Moresco | Compounds and their uses |
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| JP3326775B2 (en) * | 1992-08-25 | 2002-09-24 | 日本曹達株式会社 | Polymerization initiator composition |
| JP3937466B2 (en) * | 1995-12-28 | 2007-06-27 | 東洋インキ製造株式会社 | Energy-sensitive linear acid generator, energy-sensitive linear acid generator composition, and curable composition |
| JPH10120766A (en) * | 1996-10-21 | 1998-05-12 | Nippon Kayaku Co Ltd | Energy beam-curable composition and cured product therefrom |
| JP3950241B2 (en) * | 1997-10-17 | 2007-07-25 | 三菱重工業株式会社 | Resin composition, cured resin, and structure repair method, reinforcement method, repair material, reinforcement material |
| JP2001089639A (en) * | 1999-09-24 | 2001-04-03 | Mitsubishi Heavy Ind Ltd | Energy ray-curing resin composition |
| JP2002097443A (en) * | 2000-09-21 | 2002-04-02 | Hitachi Chem Co Ltd | Adhesive composition, circuit-connecting material using the same, and connected body |
| JP2008308569A (en) | 2007-06-14 | 2008-12-25 | Toyobo Co Ltd | Method for producing copolyester |
| JP5190665B2 (en) * | 2007-06-15 | 2013-04-24 | デクセリアルズ株式会社 | Epoxy resin composition |
| JP5444702B2 (en) * | 2008-12-05 | 2014-03-19 | デクセリアルズ株式会社 | Novel sulfonium borate complex |
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| KR101192672B1 (en) | 2012-10-19 |
| JP2011252139A (en) | 2011-12-15 |
| JP4784698B1 (en) | 2011-10-05 |
| WO2011138868A1 (en) | 2011-11-10 |
| CN102762629A (en) | 2012-10-31 |
| KR20120070619A (en) | 2012-06-29 |
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